Patent GB-410814-A (GB)
Title: Manufacture of colouring matters from o-arylene dicyanides
IPC: C09B47/067
Filed: 1932-11-16
Abstract: Nitrogen-containing colouring matters of complex constitution, and similar to the products obtainable by the processes of Specifications 322,169, [Class 2 (iii)], 389,842 and 390,149, are obtained by heating an o-phenylene- or o-naphthylene-dicyanide with or without the addition of a metal, a metal compound, ammonia or an ammonium salt.  The dicyanide may be produced and, without isolation, heated to obtain the desired colouring matter.  The production of colouring matters by heating o - dibromobenzene, 4 : 5 - dibromo - 1 : 2 - dimethylbenzene or 1 : 2-dibromonaphthalene with cuprous cyanide in pyridine or by heating phthalonitrile with cuprous bromide in pyridine is disclaimed.  The following examples are specified.  (1) Pure Phthalonitrile is heated in a sealed vessel for 7 hours at 350--360 DEG  C.; the cooled mass is finely ground, extracted with boiling acetone and purified from sulphuric acid to obtain a dark greenish blue pigment.  (2) Phthalonitrile (4 mols.) is heated with precipitated copper (1 atom) at 180--250 DEG  C.; the mass is freed from excess phthalonitrile by boiling with alcohol and is purified from sulphuric acid to obtain a greenish blue pigment containing copper.  (3) Phthalonitrile is heated with cuprous chloride in a stream of nitrogen; the mass is extracted successively with boiling water, dilute acid and alcohol to obtain a bright blue pigment which is substantially the same as the product of (2); the copper or cuprous chloride in examples (2) and (3) may be replaced by cuprous or cupric oxide, or cupric sulphide, chloride, acetate or sulphate; when cupric chloride is used, the product contains chlorine.  (4) Phthalonitrile is heated for \ba1/2\be hour at about the boiling-point with zinc chloride; the melt is extracted successively with alcohol, water and alcohol to obtain a bluish green colouring matter containing zinc.  (5) A table is given showing the character of the product when phthalonitrile is heated for specified times at specified temperatures with specified amounts of (a) stannous chloride, (b) cobaltous chloride, (c) nickelous chloride, (d) aluminium chloride, (e) barium chloride, (f) copper nitrate, (g) antimony, (h) molybdenum trioxide.  (6) Sodium is dissolved in boiling amyl alcohol, phthalonitrile is added, boiling is continued for \ba1/2\be hour; the amyl alcohol is distilled off and the residue is extracted twice with boiling alcohol to obtain a blue-green colouring matter containing some sodium.  (7) Sodium is dissolved in cyclohexanol, phthalonitrile is added and boiling is continued for \ba1/4\be hour; the resulting precipitate is separated, extracted at least twice with boiling alcohol, dissolved in concentrated sulphuric acid and precipitated by dilution to obtain a blue-green colouring matter free from metal.  (8) Potassium is dissolved in cold amyl alcohol, phthalonitrile is added and the mixture is heated for a few minutes; the cooled melt is extracted successively with alcohol, dilute acid, water and alcohol, dried, and purified from concentrated sulphuric acid to obtain a blue-green colouring matter free from metal.  (9) A mixture of calcium turnings, amyl alcohol and phthalonitrile is heated for 5 hours under reflux and the product is isolated as in (8).  (10) A solution of phthalonitrile in quinoline is heated for 3 hours at 250 DEG  C. while passing through it a stream of ammonia; the mixture is filtered hot and the residue extracted with alcohol and acetone to obtain a blue colouring matter free from metal.  (11) A solution of phthalonitrile in dimethylaniline is heated for 5 hours at or just below 250 DEG  C. which passing through it a stream of ammonia; the cooled mixture is filtered off and extracted with alcohol; the product appears to be the same as in (10).  (12) A solution of phthalonitrile in quinoline, with an addition of magnesia, is heated for 7 hours at about 220--230 DEG  C. while passing through it a stream of ammonia; the cooled mixture is extracted successively with acetone and dilute hydrochloric acid to obtain a blue colouring matter containing magnesium.  (13) Air is mixed with the ammonia in (12); the same product is obtained. (14) Phthalonitrile is heated for 2 hours at 260 DEG  C. in an atmosphere of ammonia to obtain a blue-green colouring matter. (15) 4-Chlorophthalonitrile (4 mols.) is heated with copper (1 atom) for 5--10 mins. at 220 DEG  C.; the resulting blue colouring matter is purified from concentrated sulphuric acid.  (16) 3- or 4-Nitrophthalonitrile is heated to 220 DEG  C. in a -methylnaphthalene; the latter is then removed by steam distillation and the residue is purified with concentrated sulphuric acid.  (17) 1 : 2-Dicyanonaphthalene is heated for 5 hours at 260--270 DEG  C. with copper powder and naphthalene; the product is ground and boiled with xylene to remove naphthalene and unchanged dicyanonaphthalene; the residue is purified by dissolving in concentrated sulphuric acid and diluting; the naphthalene may be replaced by a -chloronaphthalene or anthracene. (18) A colouring matter corresponding with the product of (17), but free from copper, is obtained by heating 1 : 2 - dicyanonaphthalene with sodium and amyl alcohol as in (6).  (19) 1 : 2-Dicyanonaphthalene is heated with cuprous chloride for a few minutes at 210 DEG  C. and thereafter for \ba1/2\be hour at 225 DEG C.; the cooled product is extracted successively with boiling alcohol, water, ammonia and alcohol.